Copper coordination polymers

The ligand 2,5-bis(2-pyridyl)pyrazine was used in the synthesis of a range of zinc compounds to contrast with copper coordination polymers prepared with this ligand.169 Three zinc compounds were structurally characterized, [ZnCl2L(DMF)], [Zn3(OAc)6L2], and [Zn3Cl6L3] respectively a distorted square planar monomer, a linear trimer, and a triangular arrangement of zinc centers. 

In the case of Cu(l) ions, the structure is composed of macrocations [Cu(cw-dbe)2]" in which each metal center is coordinated with one CN group of the four DTE molecules [63]. Each c/s-dbe bridges two copper(l) ions with two cyano groups, leading to an infinite network of metal cations. This copper coordination polymer shows reversible photochromism in the crystalline phase, whereas no modification is observed for the related [Cu(fra s-dbe)(THF)(C104)] which forms a zigzag chain (Fig. 6). 

Scheme 2 Constitutionally dynamic chemistry for the lanthanide-copper-glycinato coordination polymers, showing metalloligands a-f...

Lahn B, Rehahn M. Coordination polymers from kinetically labile copper(I) and silver(I) complexes true macromolecules or solution aggregates Macromol Symp 2001 163 157-176. 

It has been suggested that the copper acetylides are coordination polymers, with intermolecular interaction between the C C bonds of the acetylides and copper atoms as shown in (XL) (13). The chains may be broken with tertiary phosphines (PR s) to give complexes of the type [CuC -CR(PR 3)]4. The X-ray structure of the complex [CuC CPh(PMe3)]4 has some very interesting and unexpected features (46a)-, see structure (XL). 

Bis-Azolylazine Derivatives as Supramolecular Synthons for Copper and Silver [2 x 2] Grids and Coordination Polymers... 

Leznoff and co-workers reported the structural characterization and the polymorphic nature of a gold(I)-copper(II) coordination polymer, [Cu Au(CN)2 2(dmso)2] 00 [125]. In a green polymorphic form it possessed a 1-D chain structure with five-coordinate copper(II) centers, while a 2-D corrugated sheet structure with six-coordinate copper(II) centers was characterized in the blue polymorph, both of which are linked together to form a 3-D structure via aurophilic interactions. These two polymorphs exhibited virtually identical vapochromic behavior towards water, MeCN, dioxane, dmf, pyridine and ammonia, with the formation of [Cu Au(CN)2 2(solvent)x]oc,. 

Luminescent copper- and silver-containing coordination polymers were prepared by Harvey and collaborators using 1,8-diisocyano-p-menthane (dmb) as the coordinating unit.29,30 This aliphatic diisonitrile ligand can adopt two conformations as depicted in Figure 6. 

The same group also explored the reactivity of the two asymmetric dithioether ligands with cyclohexyl (L45) and phenyl (L46) end groups toward Cul.164 Reaction of 2 (cyclohexylmethylthio)-l-thiomorpholinoethanone L45 with copper(I) iodide afforded a ID channel-type coordination polymer [Cu4I4(L45)2]n 45, interconnected by cubane-like tetranuclear Cu4I4 cluster units (Scheme 24). The mean Cu-Cu distance within the cluster cubes amounts to 2.749 A at 173 K. 

Under similar conditions, 2-D coordinated polymers of some other 1-alkyltetrazoles 31 were synthesized using copper(ll), iron(ll), and nickel(n) halides and nitrates <2002IC6468, 2002ICA(335)61, 2003M255, 2003ICA(350)57, 2003JCD3628>. In these complexes, halide and nitrate anions are included in the inner coordination sphere. 

Until recently, the information on the coordination compounds of 2-substituted tetrazoles 6 was very poor. It has been shown that reaction of mono- and binuclear 2-substituted tetrazoles with zinc(ll) perchlorate and copper(n) chloride in organic solvents gives coordination polymers 280 containing as a ligand 2H-monosubstituted tetrazole ring (Equation 50) <2002ICA(340)215, 2005ICA3949>. 

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